Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K21/00—Fireproofing materials
  • C09K21/14—Macromolecular materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/5406—Silicon-containing compounds containing elements other than oxygen or nitrogen
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/18—Fireproof paints including high temperature resistant paints

Definitions

• the invention relates to an aqueous dispersion, its Manufacture, use and products containing them.
• halogen-containing additives or comonomers optionally in combination with antimony compounds
• Flame retardants based on metal hydroxides such as Al (OH) 3 or Mg (OH) 2 generally show an insufficient effect or impair the mechanical properties of the polymer due to the high amount used.
• Phosphorus-containing flame retardants such as ammonium polyphosphate also show less effects in themselves compared to halogen compounds.
• aqueous polymer dispersions special requirements for flame retardants: these must be water soluble or water dispersible; the the Dispersion containing flame retardants must be stable, i.e. flocculation or coagulation must not occur; in the Dispersion film, the flame retardant must be stable and homogeneous be distributed.
• DE 3803030 C2 describes the use of phosphonates as flame retardants in plastics such as polyurethane, Polyvinyl chloride, polyester and epoxy resin.
• EP 0733638 A1 describes phosphorus-containing aromatic Dicarboxylic acid esters as halogen-free flame retardants for Described polyester fiber materials.
• DE OS 19508530 describes the simultaneous use of functionalized monomers and with these functional Groups of reactive phosphorus compounds in aqueous Dispersion compositions to improve flame retardancy.
• the invention was based on the object of the prior art improve and especially aqueous To provide dispersion compositions, which even without halogen and antimony compounds in the later Use, e.g. as a coating or impregnating agent, provide adequate flame protection.
• the invention was further based on the object, aqueous To provide dispersion compositions, which at the same time for the consolidation of fiber materials and Wadding and suitable for textile finishing.
• An object of the invention are aqueous dispersion according to the claim.
• Suitable water-insoluble organopolymers are preferably Homopolymers and copolymers in the form of an aqueous dispersion are present and which, if necessary at elevated temperature and / or in an alkaline medium, after drying and if necessary, form a solid film.
• water-insoluble, film-forming are also suitable Polyaddition and polycondensation polymers such as polyurethanes, Polyester, polyether (except polyethylene oxide), polyamide, Melamine formaldehyde resins, phenol formaldehyde resins, if necessary also in the form of their oligomeric precursors.
• Preferred vinyl esters are vinyl acetate, vinyl propionate, Vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methyl vinyl acetate, Vinyl pivalate and vinyl ester of ⁇ -branched Monocarboxylic acids with up to 15 carbon atoms, especially preferably 1 to 10, for example VeoVa9®-neononanoic acid vinyl ester or VeoVa10® neodecanoic acid vinyl ester.
• Vinyl esters with a high ratio are particularly preferred from O to CH, like vinyl acetate.
• Preferred methacrylic acid esters or acrylic acid esters are Methyl acrylate, methyl methacrylate, ethyl acrylate, Ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, t-butyl acrylate, n-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl acrylate.
• methacrylic acid esters or acrylic acid esters are those with a high ratio of O to CH, such as Methyl acrylate and methyl methacrylate.
• Preferred ester groups of fumaric and maleic acids are methyl, Ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, t-butyl, Hexyl, ethylhexyl, and dodecyl group.
• Particularly preferred fumaric and maleic acid esters are such with a high ratio of O to CH, such as dimethyl fumarate and Dimethyl maleate.
• the vinyl ester copolymers may optionally be 1.0 to 65 % By weight, based on the total weight of the comonomer phase, preferably ⁇ -olefins such as ethylene or propylene and / or Vinyl aromatics such as styrene and / or acrylic acid esters or Methacrylic acid esters of alcohols with 1 to 15 carbon atoms such as Methyl acrylate, methyl methacrylate, ethyl acrylate, Ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, t-butyl acrylate, n-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl acrylate and / or ethylenic unsaturated dicarboxylic acid esters or their derivatives such as Diisopropyl fumarate, the dimethyl, methyl t-butyl, Di-n-
• Acrylic acid esters or methacrylic acid esters of are preferred Alcohols with 1 to 8 carbon atoms, very particularly preferably with 1 up to 4 carbon atoms such as methyl acrylate, methyl methacrylate, Ethyl acrylate, ethyl methacrylate, propyl acrylate, Propyl methacrylate, n-butyl acrylate, t-butyl acrylate, n-butyl methacrylate, t-butyl methacrylate.
• the vinyl ester copolymers preferably contain less than 20% by weight based on the total weight of the comonomer phase, ⁇ -olefins and / or vinyl aromatics and / or acrylic acid esters or Methacrylic acid ester of alcohols with more than 4 carbon atoms and / or ethylenically unsaturated dicarboxylic acid esters of Alcohols with more than 4 carbon atoms, so that a low O to CH Ratio is created in the copolymer.
• the (meth) acrylic ester copolymers can, if appropriate 1.0 to 65% by weight, based on the total weight of the Comonomer phase, preferably ⁇ -olefins such as ethylene or Propylene and / or vinyl aromatics such as styrene and / or ethylenic unsaturated dicarboxylic acid esters or their derivatives such as Diisopropyl fumarate, the dimethyl, methyl t-butyl, dibutyl and diethyl ester of maleic acid or fumaric acid, or Contain maleic anhydride.
• ⁇ -olefins such as ethylene or Propylene and / or vinyl aromatics such as styrene and / or ethylenic unsaturated dicarboxylic acid esters or their derivatives
• Diisopropyl fumarate the dimethyl, methyl t-butyl, dibutyl and diethyl ester of maleic acid or fumaric
• the vinyl ester copolymers contain and the (meth) acrylic acid ester copolymers still 0.05 to 10.0% by weight, based on the total weight of the Comonomer mixture, preferably auxiliary monomers from the group the ethylenically unsaturated carboxylic acids, preferably Acrylic acid or methacrylic acid; from the group of ethylenic unsaturated carboxamides, preferably acrylamide; from the Group of ethylenically unsaturated sulfonic acids or their Salts, preferably vinyl sulfonic acid; and / or from the group the polyethylenically unsaturated comonomers, for example divinyl adipate, diallyl maleate, allyl methacrylate or triallyl cyanurate.
• auxiliary monomers from the group the ethylenically unsaturated carboxylic acids, preferably Acrylic acid or methacrylic acid; from the group of ethylenic unsaturated carboxamides, preferably
• auxiliary monomers crosslinking comonomers for example Acrylamidoglycolic acid (AGA), Methyl methyl acrylamidoglycolate (MAGME), N-methylol acrylamide (NMAA), N-methylol methacrylamide, N-methyl olallyl carbamate, Alkyl ethers, such as the isobutoxy ether, or Esters of N-methylol acrylamide, N-methylol methacrylamide or the N-methylolallyl carbamate.
• AGA Acrylamidoglycolic acid
• MAGME Methyl methyl acrylamidoglycolate
• NMAA N-methylol acrylamide
• N-methylol methacrylamide N-methyl olallyl carbamate
• Alkyl ethers such as the isobutoxy ether
• Esters of N-methylol acrylamide, N-methylol methacrylamide or the N-methylolallyl carbamate for example Acrylamidoglycoli
• the production of the free-radically polymerizable water-insoluble polymers preferably takes place after the Emulsion polymerization process.
• the polymerization can discontinuous or continuous, with or without use of seed latices, with presentation of all or individual Components of the reaction mixture, or under partial submission and subsequent dosing of the or individual components of the Reaction mixture, or according to the dosing process without a template be performed. All doses are preferably made in Dimensions of the consumption of the respective component.
• the Polymerization is preferably in a temperature range of 0 to 100 ° C, particularly preferably 20 to 100 ° C, very particularly preferably carried out at 30 to 90 ° C and with those for Emulsion polymerization methods commonly used initiated.
• the initiation takes place by means of the usual water-soluble radical generator, preferably in amounts of 0.01 to 3.0% by weight, based on the total weight of the Monomers can be used. All can be used as dispersants commonly used in emulsion polymerization Emulsifiers and / or protective colloids are used.
• Emulsifiers preferably both anionic, cationic and nonionic emulsifiers into consideration, as far as these are not in Protective colloid are soluble.
• Protective colloids particularly preferably in amounts of up to 15% by weight, based on the total weight of the monomers used.
• polyvinyl alcohols and their derivatives such as Vinyl alcohol / vinyl acetate copolymers, polyvinylpyrrolidones; Polysaccharides in water-soluble form such as starches (amylose and Amylopectin), cellulose, guar, tragacanthic acid, dextran, Alginates and their carboxymethyl, methyl, hydroxyethyl, Hydroxypropyl derivatives; Proteins such as casein, soy protein, Gelatin; synthetic polymers such as poly (meth) acrylic acid, Poly (meth) acrylamide, polyvinyl sulfonic acids and their water soluble copolymers; melamineformaldehydesulfonates, Naphthalene formaldehyde sulfonates, styrene maleic acid and Vinyl ether copolymers.
• polyvinyl alcohols and their derivatives such as Vinyl alcohol / vinyl acetate copolymers, polyvinylpyrrolidones; Polysaccharides
• the organopolymers are in an amount of preferably 30 to 70% by weight, particularly preferably 40 to 60% by weight, very particularly preferably 40 to 55% by weight based on the total weight of the contain aqueous dispersion.
• Atoms particularly preferably 1 to 10, very particularly preferably 1 to 4 carbon atoms, cycloalkyl radicals with preferably 3 to 10 carbon atoms, particularly preferably 5 to 6, very particularly preferably 6 carbon atoms, alkylene radicals with preferably 2 to 4 carbon atoms Atoms, aryl, aralkyl, alkylaryl radicals with preferably 6 to 18 carbon atoms, particularly preferably 6 to 12, very particularly preferably 6 to 8 carbon atoms, the radicals R also being described with ether, thioether, ester, Amide, nitrile, hydroxyl, amine, carboxyl, sulfonic acid, carboxylic anhydride and carbonyl groups can be substituted.
• silicon compounds are, for example Tetraethoxysilane, methyltri (m) ethoxysilane, Methyltripropoxysilane, methyltri (ethoxyethoxy) silane, vinyltri (methoxyethoxy) silane, (Meth) acryloxypropyltriethoxy or - trimethoxysilane, ⁇ -nitrilethyltriethoxysilane, Mercaptopropyltriethoxy or trimethoxysilane, Phenyltriethoxysilane, iso-octyltriethoxysilane, Dipropyldiethoxysilane, methylphenyldiethoxysilane, Diphenyldimethoxysilane, methylvinyltri (ethoxyethoxy) silane and their di- and / or trisiloxanes.
• Tetraethoxysilane methyltri (m) ethoxysilane, Methyltripropoxys
• Hexamethyldiethoxytrisiloxane octamethylcyclotetrasiloxane
• Tetramethyldiethoxydisilane trimethyltrimethoxydisilane
• Dimethyltetramethoxydisilane and pentamethyldisilane disiloxane.
• the silicon compounds mentioned can preferably be used as such or in the form of their hydrolysis and condensation products be used.
• the silicon compounds mentioned can be used alone or in Mixture can be used.
• organosilicon compounds can after Procedures are carried out as in Noll, chemistry and technology of the Silicone, 2nd edition 1968, Weinheim and in Houben-Weyl, Methods of Organic Chemistry, Volume E20, pp. 1782f., 2219f., Georg Thieme Verlag, Stuttgart, 1987 are described.
• the water-dispersible organosilicon compounds are preferably in an amount of 0.5 to 60% by weight, particularly preferably 0.5 to 20% by weight, very particularly preferably 0.5% by weight up to 10% by weight based on the organopolymer content.
• the emulsifiers are generally preferred in amounts of up to 10% by weight, based on the silicon compounds, used.
• the amount is preferably ⁇ 1% by weight, based on the organopolymers.
• Suitable water-soluble or dispersible Phosphorus compounds are preferably esters, amides or Esteramides of alkyl or arylphosphonic acids, the Phosphoric acid or pyrophosphoric acid, Tetrakis (hydroxyalkyl) phosphonium salts, salts of Polyphosphoric acid, especially ammonium polyphosphate or Triaryl or trialkylphosphine oxides.
• Preferred phosphorus compounds are, for example methylphosphonate, methanephosphonate, Di (m) ethylpentaerythitdiphosphonat, (M) ethyl neopentyl phosphonate, triphenyl phosphate, Tricresyl phosphate, resorcinol bis-diphenyl phosphate, Diphenylpentaerythritol diphosphate, phenylneopentylphosphate, Mono-, di- and triammonium-nitrilo-tris-methylenephosphonate, [3 - [(hydroxy-methyl) amino] -3-oxopropyl] -phosphonic acid dimethyl ester, Tetrakis (hydroxymethyl) phosphonium chloride, Ammonium polyphosphate, tritolylphosphine oxide and triphenylphosphine oxide.
• Particularly preferred phosphorus compounds are methylphosphonate, Dimethyl methanephosphonate, mono-, di- and triammonium-nitrilo-tris-methylenephosphonate, [3 - [(hydroxy-methyl) amino] -3-oxopropyl] -phosphonic acid dimethyl ester.
• the phosphorus compounds are used in amounts of preferably 0.1 to 90% by weight, particularly preferably from 0.1 to 50% by weight, entirely particularly preferably from 5 to 30% by weight, based on the total weight of the organopolymers.
• Suitable phosphorus compounds are those that additionally carry silicon in the molecule, such as diethyl 2-triethoxysilylethanephosphonate, 2-trimethoxysilyl-ethanphosphonklarediethylester, 3-trimethoxysilyl-propanphosphonklarediethylester, 2-tri [methoxyethoxy] silyl ethanphosphonklathylester and 1,3-bis [diethylphosphonoethyl] tetramethyl disiloxane.
• the phosphorus compounds with silicon in the molecule are in Amounts of preferably 0.1 to 90% by weight, particularly preferably from 0.1 to 50% by weight, very particularly preferably from 5 to 30 % Used, based on the total weight of the Organopolymers.
• the phosphorus compounds are preferred as an aqueous solution or in the form of an emulsion - for its composition the same applies as for the silicon compounds - the Polymer dispersion added.
• the phosphorus compounds mentioned can be used alone or in Mixture can be used.
• Another object of the invention is a method for Preparation of an aqueous dispersion, the ingredients be mixed together.
• the component polymer dispersion is always an aqueous one Dispersion used.
• the silicon component can be a 100% substance or used as an aqueous emulsion.
• the phosphorus component can be a 100% substance or in the case of a solid as an aqueous solution or Dispersion or in the case of a liquid as an aqueous solution or emulsion can be used.
• one aqueous polymer dispersion with an aqueous solution of Phosphorus component and an emulsion of the silicon component is mixed.
• a possibility of the method is also preferred, wherein an aqueous polymer dispersion with the 100% Phosphorus component and an emulsion of the silicon component is mixed.
• the constituents polymer dispersion, silicon component and phosphorus component are mixed with one another by stirring or shaking, the polymer dispersion preferably being introduced and the silicon component and the phosphorus component are then added.
• the silicon component and the phosphorus component are preferably mixed first and the mixture is then added to the polymer dispersion.
• the dispersions of the invention are preferably in Coating agents, impregnating agents or adhesives used. Furthermore, they are used to solidify fibrous materials or wadding used.
• the dispersion compositions can in the typical Applications are used. For example in Coating agents and fire protection paints, in adhesives or as a binder for textiles.
• Dispersion compositions for solidifying fibrous Materials such as fleeces or wadding as well as for textile finishing.
• Another object of the invention are fiber materials, which have the dispersions of the invention.
• the with the dispersion composition of the invention treated substrates are compared to the untreated ones Flame retardant substrates.
• the invention Dispersion in a dilution of preferably 5 to 40% by weight used in water.
• the dilution is the respective Equipment procedure adapted. So when spraying it is 10 up to 25% by weight, 5 to 35% by weight when splashing and in Foam application 20 to 30% by weight.
• a film was placed on the dispersion using a doctor blade level surface so that after drying a Film thickness of about 250 microns was obtained. After about 20 hours The polymer film was air-dried for 5 min at 150 ° C. Tempered drying cabinet. The film became pieces of great size 140 mm x 52 mm cut and at least 24 hours in a desiccator stored over Blaugel.
• the LOI was determined in accordance with ISO 4589, with the difference that the samples were stored in a desiccator over Blaugel for at least 24 h before the measurement.
• methyltriethoxysilane and 2.94 g of dimethylphosphonate (DMMP) were stirred into 15.8 g of the emulsion solution.
• DMMP dimethylphosphonate
• the resulting emulsion was crosslinkable in 200 g Vinyl acetate / butyl acrylate dispersion (LT 420 from Wacker-Chemie GmbH) with a fixed content of 48% and vigorous for 2 h mixed.
• the LOI of the polymer film obtained was 23.5.
• the LOI of the polymer film obtained was 24.2.
• Wacker SiP ester Diethyl triethoxysilylethanephosphate
• the resulting emulsion was in 200 g of a crosslinkable vinyl acetate / butyl acrylate dispersion (LT 420 from Wacker-Chemie GmbH) with a fixed salary of 48% stirred in and mixed vigorously for 2 h.
• the LOI of the polymer film obtained was 23.2.
• the LOI of the polymer film obtained was 22.6.
• Wacker TES-40 hydrolysis and condensation product from Tetraethoxysilane with a Si content of 40%
• 5.88 g DMMP were stirred into 31.6 g of the emulsion solution.
• the resulting emulsion was crosslinkable in 200 g Vinyl acetate / butyl acrylate dispersion (LT 420 from Wacker-Chemie GmbH) with a fixed content of 48% and vigorous for 2 h mixed.
• the LOI of the polymer film obtained was 22.7.
• the LOI of a crosslinkable vinyl acetate / butyl acrylate dispersion (LT 420 from Wacker-Chemie GmbH) without the addition of silicon- and phosphorus-containing additives was 19.5.
• the LOI of the polymer film obtained was 21.5.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Health & Medical Sciences (AREA)
• Wood Science & Technology (AREA)
• Life Sciences & Earth Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Paints Or Removers (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Fireproofing Substances (AREA)

Applications Claiming Priority (2)

Publications (3)

Family

ID=7874351

Family Applications (1)

Country Status (5)

Families Citing this family (18)

Family Cites Families (13)

• 1998
  • 1998-07-16 DE DE19832094A patent/DE19832094A1/de not_active Withdrawn
• 1999
  • 1999-05-27 DE DE59903527T patent/DE59903527D1/de not_active Expired - Fee Related
  • 1999-05-27 EP EP99109280A patent/EP0985702B1/de not_active Expired - Lifetime
  • 1999-07-14 BR BR9902794-1A patent/BR9902794A/pt not_active IP Right Cessation
  • 1999-07-14 US US09/353,692 patent/US6111002A/en not_active Expired - Fee Related
  • 1999-07-16 JP JP20366899A patent/JP3269614B2/ja not_active Expired - Fee Related

Also Published As

Similar Documents

Legal Events